EP3141527B1 - Matériau actif, batterie électrolytique non aqueuse, module de batterie, bloc-batterie et véhicule - Google Patents

Matériau actif, batterie électrolytique non aqueuse, module de batterie, bloc-batterie et véhicule Download PDF

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EP3141527B1
EP3141527B1 EP16187789.9A EP16187789A EP3141527B1 EP 3141527 B1 EP3141527 B1 EP 3141527B1 EP 16187789 A EP16187789 A EP 16187789A EP 3141527 B1 EP3141527 B1 EP 3141527B1
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active material
battery
composite oxide
lithium
nonaqueous electrolyte
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EP3141527A8 (fr
EP3141527A1 (fr
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Yasuhiro Harada
Norio Takami
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Toshiba Corp
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Toshiba Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • C01G33/006—Compounds containing, besides niobium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/204—Racks, modules or packs for multiple batteries or multiple cells
    • H01M50/207—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape
    • H01M50/211—Racks, modules or packs for multiple batteries or multiple cells characterised by their shape adapted for pouch cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/20—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders
    • H01M50/249—Mountings; Secondary casings or frames; Racks, modules or packs; Suspension devices; Shock absorbers; Transport or carrying devices; Holders specially adapted for aircraft or vehicles, e.g. cars or trains
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/574—Devices or arrangements for the interruption of current
    • H01M50/581—Devices or arrangements for the interruption of current in response to temperature
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/76—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by a space-group or by other symmetry indications
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2200/00—Safety devices for primary or secondary batteries
    • H01M2200/10—Temperature sensitive devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/548—Terminals characterised by the disposition of the terminals on the cells on opposite sides of the cell
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/133—Renewable energy sources, e.g. sunlight

Definitions

  • Embodiments described herein relate generally to an active material, nonaqueous electrolyte battery, battery pack, vehicle.
  • a nonaqueous electrolyte battery such as a lithium ion secondary battery has been developed as a high energy-density battery.
  • the nonaqueous electrolyte battery is anticipated as a power source for vehicles such as hybrid automobiles and electric cars. Attention is also paid on them as a battery for fixed power sources for applications such as averaging out the amount of electricity consumption between day and night or for smart grids. Therefore, the nonaqueous electrolyte battery is demanded to have other good performances such as rapid charge-and-discharge performances and long-term reliability, as well.
  • a nonaqueous electrolyte battery capable of rapid charge and discharge has the benefit that charging time is remarkably short, and is able to improve motive performances in hybrid automobiles. Furthermore, the battery can also efficiently recover regenerative energy from power of the vehicle.
  • Rapid charge-and-discharge becomes possible by rapid migration of electrons and lithium ions between the positive electrode and the negative electrode.
  • dendrite of metallic lithium may sometimes precipitate on the electrode. Dendrites cause internal short circuits, and as a result raise concern that heat generation and/or fires may occur
  • a battery using a metal composite oxide as a negative electrode active material in place of a carbonaceous material has been developed.
  • a battery using titanium oxide as the negative electrode active material rapid charge-and-discharge can be stably performed.
  • Such a battery also has a longer life than those using a negative electrode with carbonaceous material.
  • oxides of titanium have a higher potential (is more noble) relative to metallic lithium. Furthermore, oxides of titanium have a lower capacity per weight. Therefore, a battery using an oxide of titanium as the negative electrode active material has a problem that the energy density is lower.
  • the potential of the electrode using an oxide of titanium is about 1.5 V relative to metallic lithium and is higher (more noble) than that of the negative electrode with carbonaceous material.
  • the potential of an oxide of titanium arises from the redox reaction between Ti 3+ and Ti 4+ upon electrochemical insertion and extraction of lithium, and is therefore electrochemically limited.
  • the theoretical capacity of lithium titanate is about 165 mAh/g
  • the theoretical capacity of a lithium-titanium composite oxide such as Li 4 Ti 5 O 12 is about 180 mAh/g.
  • the theoretical capacity of a general graphite based electrode material is 385 mAh/g and greater. Therefore, the capacity density of an oxide of titanium is significantly lower than that of the carbon based negative electrode material. This is due to there being only a small number of lithium-insertion sites in the crystal structure, and lithium tending to be stabilized in the structure, and thus, substantial capacity being reduced.
  • a new electrode material including titanium (Ti) and niobium (Nb) has been examined.
  • Such materials are expected to have high charge-and-discharge capacities.
  • a composite oxide represented by TiNb 2 O 7 has a theoretical capacity exceeding 380 mAh/g; however, the substantial capacity of an electrode of TiNb 2 O 7 is about low as 260 mAh/g, and has the problem that the charge-and-discharge life is short.
  • EP 2 503 625 A2 relates to a battery active material including a complex oxide containing Nb and Ti and an element M.
  • the molar ratio (M/Ti) of the element M to Ti satisfies the following formula (I): 0 ⁇ M/Ti ⁇ 0.5 (I).
  • the molar ratio (Nb/Ti) of Nb to Ti satisfies the following formula (II): 0 ⁇ Nb/Ti ⁇ 5 (II)
  • the element M is at least one selected from the group consisting of B, Na, Mg, Al, Si, S, P, K, Ca, Mo, W, Cr, Mn, Co, Ni, and Fe.
  • EP 2 784 026 A1 relates to an active substance containing active material particles.
  • the active material particles comprise a compound represented by the formula: Ti 1-x M1 x Nb 2-y M2 y O 7 .
  • the active material particles have a peak A attributed to a (110) plane which appears at 2 ⁇ ranging from 23.74 to 24.14°, a peak B attributed to a (003) plane which appears at 2 ⁇ ranging from 25.81 to 26,21° and a peak C attributed to a (-602) plane which appears at 2 ⁇ ranging from 26.14 to 26.54° in an X-ray diffraction pattern of the active material particles.
  • An intensity I A of the peak A, an intensity I B of the peak B, and an intensity I C of the peak C satisfy the relation (1): 0.80 ⁇ I B /I A ⁇ 1.12; and the relation (2) I C /I B ⁇ 0.80.
  • an active material including a monoclinic niobium-titanium composite oxide is provided.
  • the active material a portion of or all of niobium (Nb) or titanium (Ti) as a constituent element of Nb 2 TiO 7 is substituted by an element.
  • Nb or Ti satisfies any one of following formulas (1) to (3): Ti(IV) ⁇ 0.75M(V) + 0.25M(I) (1) Ti(IV) ⁇ 0.6M(VI) + 0.4M(I) (2) Nb(V) ⁇ 0.8M(VI) + 0.2M(I) (3), where M(VI) is at least one of Mo and W, M(V) is at least one of Nb, Ta, and V, and M(I) is at least one of Na, K, Rb, and Cs.
  • a nonaqueous electrolyte battery including a negative electrode including the above active material, a positive electrode, and a nonaqueous electrolyte is provided.
  • a battery pack including the above nonaqueous electrolyte battery is provided.
  • a battery active material includes a monoclinic niobium composite oxide, and in the active material, in a crystal lattice of a niobium-titanium composite oxide Nb 2 TiO 7 , a portion of or all of niobium (Nb) at a niobium site or titanium (Ti) at a titanium site is substituted by an element M (M(VI), M(V), and M(I)), as represented by any one of the following formulas (1) to (3): Ti(IV) ⁇ 0.75M(V) + 0.25M(I) (1) Ti(IV) ⁇ 0.6M(VI) + 0.4M(I) (2) Nb(V) ⁇ 0.8M(VI) + 0.2M(I) (3), where M(VI) is at least one of Mo and W, M(V) is at least one of Nb, Ta, and V, and M(I) is at least one of Na, K, Rb, and Cs.
  • M(VI) is at least one of Mo and
  • M(VI) may be either one of Mo and W, or a combination of both Mo and W.
  • M(V) may be one of Nb, Ta, and V, or a combination of two or more of Nb, Ta, and V.
  • M(I) may be one of Na, K, Rb, and Cs, or a combination of two or more of Na, K, Rb, and Cs.
  • Niobium-titanium composite oxides primarily exhibit a monoclinic crystal structure.
  • schematic diagrams of a crystal structure of monoclinic Nb 2 Ti 0.9 (Nb 0.75 Na 0.25 ) 0.1 O 7 are shown in FIGS. 1 and 2 .
  • a metal ion 101 and an oxide ion 102 form a structural framework 103.
  • the structural frameworks 103 are alternately arranged three-dimensionally, whereby a vacancy 104 exists among the structural frameworks 103.
  • the vacancy 104 serves as a host for lithium ions.
  • the crystal structure can be represented as Li 5 Nb 2 Ti 0.9 (Nb 0.75 Na 0.25 ) 0.1 O 7 .
  • a region 105 and a region 106 are portions having two-dimensional channels in [100] and [010] directions.
  • a vacancy 107 exists in a [001] direction.
  • the vacancy 107 has a tunnel structure favorable for the conduction of lithium ions, and the vacancy 107 serves as a conductive path in the [001] direction connecting the region 105 and the region 106. This conductive path makes it possible for the lithium ions to migrate between the region 105 and the region 106.
  • the niobium-titanium composite oxide included in the battery active material in this embodiment preferably has a crystal structure having a space group C2/m symmetry and an atomic coordination described in Journal of Solid State Chemistry 53, pp. 144-147 (1984 ).
  • the embodiment is not limited to this, however.
  • the metal ion 101 composing the skeleton is reduced to a valence of 3, thereby maintaining electric neutrality of the crystal.
  • the niobium-titanium composite oxide of the embodiment not only is Ti ion reduced from a valence of 4 to a valence of 3, but Nb ion is reduced from a valence of 5 to a valence of 3, also. For this reason, the number of valence reduction per weight of the active material is large. Therefore, the niobium-titanium composite oxide can maintain electric neutrality of the crystal even if a great amount of lithium ions are inserted.
  • the energy density is higher in comparison to compounds such as titanium oxide containing only a Ti ion whose valence (in a state where lithium ions are not inserted) is tetravalent (valence of 4).
  • the niobium-titanium composite oxide has a lithium insertion potential of about 1.5 V (vs. Li/Li + ). Therefore, by virtue of the use of the active material, it is possible to provide a battery capable of repetitive rapid charge-and-discharge in stable manner.
  • the theoretical capacity of a general niobium-titanium composite oxide, TiNb 2 O 7 being a representative, is about 387 mAh/g, which is a value two or more times that of an oxide of titanium having a spinel structure.
  • the actual capacity of a niobium-titanium composite oxide that has been reported so far is lower than the theoretical capacity, and the actual capacity is confirmed to be about 260 mAh/g.
  • the inventors of the present application have found that in a niobium-titanium composite oxide, by placing into the crystal structure in advance by substitution, elements having a large ionic radius, such as sodium (Na), potassium (K), Rubidium (Rb), and Cesium (Cs), the above-described conductive path for lithium ions can be enlarged. When the crystal lattice becomes large, those conductive paths are enlarged, and therefore lithium ions become more able to migrate. Due to enlarging of the regions having a two-dimensional channel in which diffusion of lithium ions is rapid and the conductive path in the [001] direction connecting these regions, the capability to have lithium ions be inserted into and extracted from an insertion space is improved.
  • elements having a large ionic radius such as sodium (Na), potassium (K), Rubidium (Rb), and Cesium (Cs)
  • an active material including a niobium composite oxide having a composition corresponding to a compound in which a portion of or all of niobium (Nb) or titanium (Ti) in the niobium-titanium composite oxide Nb 2 TiO 7 is substituted by an element M (M(VI), M(V), and M(I)), in such a manner that any one of the following formulas (1) to (3) is satisfied.
  • M(VI) is at least one of Mo and W
  • M(V) is at least one of Nb, Ta, and V
  • M(I) is at least one of Na, K, Rb, and Cs.
  • the valence of M(VI) is 6
  • the valence of M(V) is 5
  • the valence of M(I) is 1.
  • M(VI) may be either one of Mo and W, or a combination of both Mo and W.
  • M(V) may be one of Nb, Ta, and V, or a combination of two or more of Nb, Ta, and V.
  • M(I) may be one of Na, K, Rb, and Cs, or a combination of two or more of Na, K, Rb, and Cs.
  • the numerical values 0.75 and 0.25 in the formula represent numerical values based on a stoichiometric ratio for maintaining electric charge to neutral. Since a compound of the embodiment includes transition metals, even if the numerical value is deviated within a range of about ⁇ 6%, the electric charge can be kept neutral by oxidation-reduction of the transition metals, and therefore, an active material having a desired crystal phase can be obtained. However, since the deviation of the numerical value affects a chargeable capacity, it is preferable that the deviation of numerical value is less than 3%.
  • the state in which a battery is completely discharged indicates a state in which an electrode including the compound is held for 1 hour or more at a potential of +3.0 V with respect to the potential of metallic lithium to thereby extract mobile lithium ions from the compound.
  • an electrode including the compound is taken out.
  • a three-pole half-cell with lithium metal as a counter electrode and a reference electrode is composed.
  • the electrode works as a positive electrode with respect to lithium metal negative electrode.
  • a current is flown in a charging direction (a direction where lithium is extracted from the electrode) using a charging/discharging device until the cell potential reaches 3.0 V. Once the cell potential has reached 3.0 V, the potential is maintained further at this value for 1 hour or more to perform extraction of lithium ions from the electrode including the compound, whereby the state in which the battery is completely discharged can be achieved.
  • the niobium composite oxide is preferably represented by any one of the following general formulas (A) to (E) : Nb 2 Ti 1-y (M(V) 0.75 M(I) 0.25 ) y O 7 (A) Nb 2 Ti 1-y (M(VI) 0.6 M(I) 0.4 ) y O 7 (B) Nb 2-x (M(VI) 0.8 M(I) 0.2 ) x TiO 7 (C) Nb 2-x (M(VI) 0.8 M(I) 0.2 ) x Ti 1-y (M(V) 0.75 M(I) 0.25 ) y O 7 (D) Nb 2-x (M(VI) 0.8 M(I) 0.2 ) x Ti 1-y (M(VI) 0.6 M(I) 0.4 ) y O 7 (E), where M(VI) is at least one of Mo and W, M(V) is at least one of Nb, Ta, and V, M(I) is at least one of Na, K, Rb
  • M(VI) may be either one of Mo and W, or a combination of both Mo and W.
  • M(V) may be one of Nb, Ta, and V, or a combination of two or more of Nb, Ta, and V.
  • M(I) may be one of Na, K, Rb, and Cs, or a combination of two or more of Na, K, Rb, and Cs.
  • the subscript value y is 0.1 or more, the Ti site is sufficiently substituted, and improvement in the above-described performances can be expected for the active material of the embodiment.
  • the subscript value y is more than 0.9, and especially when the value is 1, since Ti within the active material becomes insufficient, a high capacity may not be obtained.
  • the subscript value x is 1.0 or more, the Nb site sufficiently substituted, and improvement in the performances of the active material of the embodiment can be expected.
  • All compounds represented by the above general formulas (A) to (E) have a crystal structure capable of having lithium inserted.
  • lithium ions may be inserted into the compounds in accompany with the charge and discharge of the battery.
  • the above general formulas (A) to (E) can be represented by the following general formulas (A') to (E') : Li a Nb 2 Ti 1-y (M(V) 0.75 M(I) 0.25 ) y O 7 (A') Li a Nb 2 Ti 1-y (M(VI) 0.6 M(I) 0.4 ) y O 7 (B') Li a Nb 2-x (M(VI) 0.8 M(I) 0.2 ) x TiO 7 (C') Li a Nb 2-x (M(VI) 0.8 M(I) 0.2 ) x Ti 1-y (M(V) 0.75 M(I) 0.25 ) y O 7 (D') Li a Nb 2-x (M(VI) 0.8 M(I) 0.2 ) x Ti 1-y (M(VI) 0.6 M(I) 0.4 ) y O 7 (E'), where M(VI) is at least one of Mo and W
  • M(VI) may be either one of Mo and W, or a combination of both Mo and W.
  • M(V) may be one of Nb, Ta, and V, or a combination of two or more of Nb, Ta, and V.
  • M(I) may be one of Na, K, Rb, and Cs, or a combination of two or more of Na, K, Rb, and Cs.
  • the subscript a may change within a range of 0 ⁇ a ⁇ 5 by insertion and extraction of lithium into and from the active material in accompany with charge and discharge of the battery.
  • the subscript a indicates an amount of lithium ions included in the compound as an active material.
  • the lithium insertion sites in the above-described monoclinic crystal structure can stably maintain their structure, even if a lattice constant is changed by insertion of lithium maintained.
  • Nb and Ti, and M(V) and M(VI), which substitute them, may all exist within equivalent crystal sites at a uniform proportion.
  • that the crystal sites are equivalent means that they exist at positions where the symmetry within a crystal is equivalent.
  • any of Nb, Ti, M(V), and M(VI) may exist at the same probability.
  • that the various elements exist within an equivalent crystal site at a uniform proportion means that an uneven distribution of elements within the crystal site does not occur. Namely, the various elements are stochastically disposed evenly amongst all the crystal sites of which they occupy. In other words, Nb, Ti, M(V), and M(VI) are randomly arranged within occupancy sites in the crystal structure.
  • Na, K, Rb, and Cs which are M(I), are elements having ion radii larger than those of Nb, Ti, M(V) and M(VI). These M(I) elements may exist at the above-described sites equivalent to Nb and Ti, or at a crystal site equivalent to a lithium insertion site.
  • a composite oxide including M(I) element having a larger ion radius can have a crystal lattice having a larger volume.
  • a nonaqueous electrolyte battery using, as an active material, a composite oxide capable of having a crystal lattice having a large volume can have further improved repetitive charge-and-discharge performances, and as a result, can exhibit more excellent life performance. This is because by increasing the lattice volume in advance, expansion and contraction of the crystal lattice that occur when lithium ions are inserted and extracted is suppressed, and cracking of crystal and peeling from an electrode current collector can be suppressed.
  • the tetravalent element means an element whose valence is 4 in a state in which lithium ion is not electrochemically inserted into the composite oxide and is represented by M(IV).
  • a lattice constant can be enhanced by randomly substituting Zr, Hf, Ge, and Sn as M(IV) into Ti sites.
  • those except for Sn do not have an electrochemical activity at a potential at which lithium can be inserted and extracted, and are not involved in oxidation and reduction that accompany insertion and extraction of lithium.
  • an amount of substitution using those elements is preferably half (corresponding to 0.5 mol) or less with respect to the Ti sites.
  • a compound represented by Li a Nb 2 Ti 1-y (M(V) 0.75 M(I) 0.25 ) y O 7 Ti is further substituted by M(IV).
  • the range of the subscript z can be expanded to a range of 0 to 1, and the composition becomes Li a Nb 2 M(IV) z Ti 1-y-z (M(V) 0.75 M(I) 0.25 ) y O 7 (0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, and 0 ⁇ a ⁇ 5).
  • the composite oxide represented by the above general formulas does not theoretically include lithium in a completely discharged state. Actually however, after a battery including, as an active material, the composite oxide represented by the above general formulas is charged and discharged once, lithium may remain in the crystal structure of the composite oxide even in a discharged state.
  • the battery active material according to the first embodiment can realize a nonaqueous electrolyte battery capable of exhibiting excellent rapid charge-and-discharge performances and repetitive charge-and-discharge performances even in a state in which lithium exists in the crystal structure.
  • An average particle diameter of a composite oxide included in the battery active material according to the first embodiment is not particularly limited and can be changed according to desired battery properties.
  • the average particle diameter of the composite oxide may be 0.1 to 10 ⁇ m. If the average particle diameter is more than 0.1 ⁇ m, the crystal structure can be stabilized by enhancing the crystallinity. Meanwhile, by having the average particle diameter be less than 10 ⁇ m, movement of lithium ions within the crystal can be facilitated.
  • the composite oxide there may be formed secondary particles that are formed of primary particles having such an average particle diameter.
  • the average particle diameter of the secondary particles is 1 to 30 ⁇ m, for example. When the average particle diameter of the secondary particles is 1 ⁇ m or more, an electrode coating liquid can be stabilized. When the average particle diameter of the secondary particles is less than 30 ⁇ m, the active material becomes applicable to a design having a reduced electrode film thickness.
  • the BET specific surface area of the composite oxide included in the battery active material according to the first embodiment is not particularly limited, and is preferably 0.1 m 2 /g or more and less than 100 m 2 /g.
  • the BET specific surface area is 0.1 m 2 /g or more, the contact area with the electrolytic solution can be secured. Thus, good discharge rate performances can be easily obtained and also, a charge time can be shortened.
  • the BET specific surface area is less than 100 m 2 /g, reactivity with the electrolytic solution can be prevented from becoming too high and therefore, the life performance can be improved.
  • the BET specific surface area is 100 m 2 /g or less, a coatability of a slurry including the active material used in the production of an electrode, which will be described later, can be improved.
  • the composition of the battery active material can be analyzed using Inductively Coupled Plasma (ICP) emission spectrometry, for example.
  • ICP Inductively Coupled Plasma
  • the abundance ratios of elements depend on the sensitivity of the analyzing device that is used. Therefore, the numerical values may deviate from the element ratios disclosed in the present application, by a value in accordance to errors of the measuring device. However, even if the measurement results deviate within the error range of the analyzing device, effects of the present application can be sufficiently exhibited.
  • a solid solution state of metal M in a composite oxide can be examined by transmission electron microscope (TEM) observation - energy dispersive X-ray spectroscopy (EDX).
  • TEM transmission electron microscope
  • EDX energy dispersive X-ray spectroscopy
  • the crystal structure of a composite oxide included in the battery active material can be examined, for example by combining a powder X-ray diffraction (XRD) measurement and analysis according to a Rietveld method.
  • XRD powder X-ray diffraction
  • the powder X-ray diffraction measurement of the active material may be performed, for example, as follows.
  • the active material is ground to prepare a sample with average particle size of approximately 5 ⁇ m or less.
  • the average particle size can be obtained by laser diffraction.
  • the obtained sample is filled in a holder part having a depth of 0.2 mm, formed on a glass sample plate.
  • the surface of the filled sample is flattened by pressing with another glass plate.
  • the glass plate filled with the sample is set in a powder X-ray diffractometer. And then, an XRD pattern is obtained using Cu-K ⁇ rays.
  • Such a sample having significantly high orientation is measured using a capillary. Specifically, the sample is inserted into the capillary, which is then mounted on a rotary sample table and measured. Such a measuring method can reduce the influence of orientation.
  • the capillary one made of Lindemann glass is used.
  • the X-ray diffraction (XRD) pattern obtained herein must be applicable to Rietveld analysis.
  • the measurement time or X-ray intensity is appropriately adjusted in such a manner that the step width is made 1/3 to 1/5 of the minimum half width of the diffraction peaks and the intensity at the peak position of strongest reflected intensity is 5,000 counts to 10000 counts.
  • the obtained XRD pattern obtained is analyzed by the Rietveld method.
  • the diffraction pattern is calculated from the crystal structure model which has been previously estimated.
  • the parameters of the crystal structure (lattice constant, atomic coordinate, crystal site occupancy ratio, or the like) can be precisely analyzed by fitting all the calculated values with the measured values. Thereby, the characteristics of the crystal structure of the synthesized oxide can be determined. Furthermore, the site occupancy ratio of constitutional elements in each of the sites can be determined.
  • a fitting parameter S is used as the scale for estimating the degree of agreement between the measured intensities and the calculated intensities in the Rietveld analysis.
  • the S value must be less than 1.8 in the analysis.
  • the standard deviation ⁇ j must be taken into consideration.
  • the fitting parameter S and standard deviation ⁇ j defined herein are estimated using the formula described in " Funmatsu X sen Kaisetsu no Jissai (Reality of Powder X-Ray Analysis)", X-Ray Analysis Investigation Conversazione, The Japan Society for Analytical Chemistry, written and edited by Izumi Nakai and Fujio Izumi (Asakura Publishing Co., Ltd. ).
  • the measurement of the specific surface area of the composite oxide included in the battery active material according to the first embodiment may be performed by a method where molecules, in which an occupied area in adsorption is known, are adsorbed onto the surface of powder particles at the temperature of liquid nitrogen and determining the specific surface area of the sample from the amount of adsorbed molecules.
  • the most frequently used method is a BET method based on the low temperature/low humidity physical adsorption of an inert gas.
  • the basic theory of the BET method is the most well-known theory of the method of calculating the specific surface area in which the Langmuir theory, which is a monolayer adsorption theory, is extended to multilayer adsorption.
  • the specific surface area determined by the above method is referred to as "BET specific surface area”.
  • the active material is put in a state in which lithium ions are completely extracted from a composite oxide.
  • a battery including the negative electrode active material is brought into a state in which the electrode is completely discharged.
  • lithium ions remaining in the negative electrode active material may exist.
  • the battery is disassembled in a glove box filled with argon, and the electrode is taken out.
  • the thus taken out electrode is washed with a suitable solvent.
  • a suitable solvent ethyl methyl carbonate may be used, for example.
  • the electrode washed as described above is cut out to have an area equivalent to an area of a holder of a powder X-ray diffraction device, so that the cut-out electrode can be used as a measurement sample. Measurement is performed with this sample applied directly onto a glass holder.
  • an electrode layer may be physically dislodged from the current collector.
  • the electrode layer By applying ultrasonic waves in a solvent, the electrode layer can be easily peeled from the current collector.
  • An electrode powder sample may be prepared from the electrode layer thus peeled and subjected to various measurements.
  • a peak corresponding to metal of metal foil included, as a current collector, in the electrode is measured in advance using XRD, and a peak position derived from an electrode current collector is taken note of.
  • the peak positions of other components such as a conductive auxiliary agent and a binder are also measured in advance by a similar method, and taken note of.
  • the peeled active material-including layer is sealed in a capillary and placed on a rotating sample stage, whereby measurement is performed. According to such a method, an XRD pattern of the active material can be obtained with an influence of orientation being reduced. Of course, if these peaks can be taken note of in advance, such an operation may be omitted.
  • contamination by an impurity phase such as of lithium carbonate and lithium fluoride may be observed in results of the powder X-ray diffraction measurement.
  • the contamination by the impurity phase can be prevented, for example by using an inert gas atmosphere as the measurement atmosphere or washing the electrode surface. Even if impurity phases exist, analysis can be performed ignoring these phases.
  • the electrode When performing the ICP measurement, the TEM-EDX measurement, and the measurement of a specific surface area with the use of a BET method for the active material included in the electrode that is taken out from the battery and washed, the electrode is cut out to have a suitable size, or the active material is peeled from the current collector to be used as a measurement sample, as in the powder X-ray diffraction measurement.
  • the active material of the embodiment can be produced by the following method.
  • a starting material is mixed.
  • oxides or salts including Li, Ti, and Nb are used as starting materials for a niobium-titanium composite oxide.
  • the salt used as the starting material is preferably salt such as carbonates and nitrates, which decomposes at a relatively low temperature to produce an oxide.
  • the starting material is mixed at an element ratio such that a desired composition would be achieved. Then, the obtained mixture is pulverized to obtain a mixture that is uniform as much as possible. Subsequently, the obtained mixture is calcined. The calcining is performed within a temperature range of 500 to 1450°C, divided into two or more steps for a total of 10 to 40 hours. After calcining, the calcined product is immediately taken out from the electric furnace and then cooled to room temperature. Preferably, the calcined product is cooled under a condition such that the temperature of the calcined product lowers from the calcining temperature to 100°C or less within 1 hour. Thus, an electrode active material including the desired niobium-titanium composite oxide can be obtained.
  • lithium ions may be inserted by charging a battery including the composite oxide as a negative electrode active material.
  • the niobium-titanium composite oxide may be synthesized as a composite oxide including lithium by using, as a starting material, a lithium-including compound such as lithium carbonate.
  • the niobium composite oxide including M(I) elements and M(V) elements or M(VI) elements at a specific inclusion ratio, there can be provided an active material having high energy density and high rapid charge-and-discharge performances and excellent in life performance.
  • a nonaqueous electrolyte battery including a negative electrode that includes the active material according to the above described first embodiment, a positive electrode, and a nonaqueous electrolyte, a separator, and a container member.
  • the negative electrode includes a current collector and a negative electrode layer (that is, a negative electrode active material-including layer).
  • the negative electrode layer is formed on one surface or reverse surfaces of the current collector.
  • the negative electrode layer includes an active material, and optionally a conductive agent and a binder.
  • the battery active material described in the first embodiment is used. Accordingly, it is possible to provide a battery excellent in productivity and having excellent rapid charge-and-discharge performances and high energy density.
  • the battery active material according to the first embodiment may be singly used as the negative electrode active material; however, another active material may also be used in combination.
  • Other active materials include titanium dioxide (TiO 2 ) having an anatase structure, lithium titanate having a ramsdellite structure (e.g., Li 2 Ti 3 O 7 ), a lithium titanate having a spinel structure (e.g., Li 4 Ti 5 O 12 ).
  • TiO 2 titanium dioxide
  • Li 2 Ti 3 O 7 lithium titanate having a ramsdellite structure
  • Li 4 Ti 5 O 12 Li 4 Ti 5 O 12
  • One kind of the other active materials may be used singly, or two or more kinds of the other active materials may be used in combination.
  • the conductive agent is added to improve a current collection performance and to suppress the contact resistance between the active material and the current collector.
  • Examples of the conductive agent include carbonaceous substances such as acetylene black, carbon black, and graphite.
  • the binder is added to fill gaps among the dispersed negative electrode active material and also to bind the active material with the current collector.
  • the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine rubber, and styrene-butadiene rubber.
  • the active material, conductive agent and binder in the negative electrode layer are preferably blended in proportions of 68% by mass to 96% by mass, 2% by mass to 30% by mass, and 2% by mass to 30% by mass, respectively.
  • amount of conductive agent is 2% by mass or more, the current collection performance of the negative electrode layer can be improved.
  • amount of binder is 2% by mass or more, binding between the negative electrode layer and current collector becomes sufficient, and excellent cycling performances can be expected.
  • an amount of each of the conductive agent and binder is preferably 28% by mass or less, in attempting to increase the capacity.
  • the current collector a material which is electrochemically stable at the lithium insertion and extraction potential of the negative electrode active material is used.
  • the current collector is preferably made of copper, nickel, stainless steel or aluminum, or an aluminum alloy including one or more elements selected from Mg, Ti, Zn, Mn, Fe, Cu, and Si.
  • the thickness of the current collector is preferably 5 ⁇ m to 20 ⁇ m. The current collector having such a thickness can maintain balance between the strength and weight reduction of the negative electrode.
  • the negative electrode is produced by, for example, suspending a negative electrode active material, a binder, and a conductive agent in an ordinarily used solvent to prepare a slurry, applying the slurry to a current collector, drying the coating to form a negative electrode layer, and then pressing the layer.
  • the negative electrode may also be produced by forming a negative electrode active material, a binder, and a conductive agent into pellets as the negative electrode layer, and disposing the pellets onto a current collector.
  • the positive electrode includes a current collector and a positive electrode layer (that is, positive electrode active material-including layer).
  • the positive electrode layer is formed on one surface or reverse surfaces of the current collector.
  • the positive electrode layer includes a positive electrode active material, and optionally a conductive agent and a binder.
  • an oxide or a sulfide may be used as the positive electrode active material.
  • the oxide and sulfide include manganese dioxide (MnO 2 ), iron oxide, copper oxide, nickel oxide, lithium manganese composite oxide (e.g., Li x Mn 2 O 4 or Li x MnO 2 ), lithium nickel composite oxide (e.g., Li x NiO 2 ), lithium cobalt composite oxide (e.g., Li x CoO 2 ), lithium nickel cobalt composite oxide (e.g., LiNi 1-y Co y O 2 ), lithium manganese cobalt composite oxide (e.g., Li x MnyCo 1-y O 2 ), lithium manganese nickel composite oxide having a spinel structure (e.g., Li x Mn 2-y Ni y O 4 ), lithium phosphorus oxide having an olivine structure (e.g., Li x FePO 4 , Li x Fe 1-y Mn y PO 4 , and Li x CoPO 4
  • the active material include lithium manganese composite oxide (e.g., Li x Mn 2 O 4 ), lithium nickel composite oxide (e.g., Li x NiO 2 ), lithium cobalt composite oxide (e.g., Li x CoO 2 ), lithium nickel cobalt composite oxide (e.g., LiNi 1-y Co y O 2 ), lithium manganese nickel composite oxide having a spinel structure (e.g., Li x Mn 2-y Ni y O 4 ), lithium manganese cobalt composite oxide (e.g., Li x Mn y Co 1-y O 2 ), lithium iron phosphate (e.g., Li x FePO 4 ), and lithium nickel cobalt manganese composite oxide, which have a high positive electrode voltage.
  • lithium manganese composite oxide e.g., Li x Mn 2 O 4
  • Li x NiO 2 lithium cobalt composite oxide
  • LiNi 1-y Co y O 2 lithium manganese nickel composite oxide having a spinel structure (e
  • the active material include lithium iron phosphate, Li x VPO 4 F (0 ⁇ x ⁇ 1), lithium manganese composite oxide, lithium nickel composite oxide, and lithium nickel cobalt composite oxide. Since these compounds have low reactivity with ordinary temperature molten salts, cycle life can be improved.
  • the primary particle size of the positive electrode active material is preferably 100 nm to 1 ⁇ m.
  • the positive electrode active material having a primary particle size of 100 nm or more is easy to handle during industrial production. In the positive electrode active material having a primary particle size of 1 ⁇ m or less, diffusion of lithium ions within solid can proceed smoothly.
  • the specific surface area of the positive electrode active material is preferably 0.1 m 2 /g to 10 m 2 /g.
  • the positive electrode active material having a specific surface area of 0.1 m 2 /g or more can secure sufficient sites for inserting and extracting lithium ions.
  • the positive electrode active material having a specific surface area of 10 m 2 /g or less is easy to handle during industrial production, and can secure a good charge and discharge cycle performance.
  • the binder is added to bind the active material with the current collector.
  • the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluorine rubber.
  • the conductive agent is added as necessary, in order to improve the current collection performance, and at the same time, suppress the contact resistance between the active material and current collector.
  • Examples of the conductive agent include carbonaceous substances such as acetylene black, carbon black, and graphite.
  • the active material and binder are preferably included in proportions of 80% by mass to 98% by mass, and 2% by mass to 20% by mass, respectively.
  • the amount of the binder is 2% by mass or more, sufficient electrode strength can be achieved.
  • the amount of the binder is 20% by mass or less, the amount of the insulator in the electrode can be reduced, and thereby the internal resistance can be decreased.
  • the active material, binder, and conductive agent are preferably included in proportions of 77% by mass to 95% by mass, 2% by mass to 20% by mass, and 3% by mass to 15% by mass, respectively.
  • the amount of the conductive agent is 3% by mass or more, the above-described effects can be expressed.
  • the amount of the conductive agent is 15% by mass or less, the decomposition of a nonaqueous electrolyte on the surface of the positive electrode conductive agent during high-temperature storage can be reduced.
  • the current collector is preferably an aluminum foil, or an aluminum alloy foil including one or more elements selected from Mg, Ti, Zn, Ni, Cr, Mn, Fe, Cu, and Si.
  • the thickness of the aluminum foil or aluminum alloy foil is preferably 5 ⁇ m to 20 ⁇ m, and more preferably 15 ⁇ m or less.
  • the purity of the aluminum foil is preferably 99% by mass or more.
  • the amount of the transition metal such as iron, copper, nickel, or chromium included in the aluminum foil or aluminum alloy foil is preferably 1% by mass or less.
  • the positive electrode is produced by, for example, suspending an active material, a binder, and a conductive agent, which is added as necessary, in an appropriate solvent to prepare a slurry, applying the slurry to a positive electrode current collector, drying the coating to form a positive electrode layer, and then pressing the layer.
  • the positive electrode may also be produced by forming an active material, a binder, and a conductive agent, which is added as necessary, into pellets as the positive electrode layer, and disposing the pellets onto a current collector.
  • the nonaqueous electrolyte may be, for example, a liquid nonaqueous electrolyte which is prepared by dissolving an electrolyte in an organic solvent, or gel like nonaqueous electrolyte which is a composite of a liquid electrolyte and a polymer material.
  • the liquid nonaqueous electrolyte is preferably prepared by dissolving an electrolyte in an organic solvent at a concentration of 0.5 mol/L to 2.5 mol/L.
  • Examples of the electrolyte include lithium salts such as lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), and lithium bistrifluoromethylsulfonylimide (LiN(CF 3 SO 2 ) 2 ), and mixtures thereof.
  • the electrolyte is preferably resistant to oxidation even at a high potential, and most preferably LiPF 6 .
  • organic solvent examples include a cyclic carbonate such as propylene carbonate (PC), ethylene carbonate (EC), or vinylene carbonate (VC); a linear carbonate such as diethyl carbonate (DEC), dimethyl carbonate (DMC), or methyl ethyl carbonate (MEC); a cyclic ether such as tetrahydrofuran (THF), 2-methyl tetrahydrofuran (2-MeTHF), or dioxolane (DOX); a linear ether such as dimethoxy ethane (DME) or diethoxy ethane (DEE); ⁇ -butyrolactone (GBL), acetonitrile (AN), and sulfolane (SL).
  • a cyclic carbonate such as propylene carbonate (PC), ethylene carbonate (EC), or vinylene carbonate (VC)
  • a linear carbonate such as diethyl carbonate (DEC), dimethyl carbonate (DMC), or methyl eth
  • polymeric material examples include polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), and polyethylene oxide (PEO).
  • PVdF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • PEO polyethylene oxide
  • the nonaqueous electrolyte may be, for example, an ordinary temperature molten salt (ionic melt) including lithium ions, a polymer solid electrolyte, or an inorganic solid electrolyte.
  • the ordinary temperature molten salt means compounds among organic salts made of combinations of organic cations and anions, which are able to exist in a liquid state at ordinary temperature (15 to 25°C).
  • the ordinary temperature molten salt includes an ordinary temperature molten salt which exists alone as a liquid, an ordinary temperature molten salt which becomes a liquid upon mixing with an electrolyte, and an ordinary temperature molten salt which becomes a liquid when dissolved in an organic solvent.
  • the melting point of the ordinary temperature molten salt used in nonaqueous electrolyte batteries is 25°C or below.
  • the organic cations generally have a quaternary ammonium framework.
  • the polymer solid electrolyte is prepared by dissolving the electrolyte in a polymeric material, and solidifying it.
  • the inorganic solid electrolyte is a solid substance having lithium ion conductivity.
  • the separator may be made of, for example, a porous film or synthetic resin nonwoven fabric including polyethylene, polypropylene, cellulose, or polyvinylidene fluoride (PVdF).
  • a porous film formed from polyethylene or polypropylene melts at a fixed temperature and thus able to shut off a current, therefore the porous film can improve safety.
  • a laminate film having a thickness of 0.5 mm or less, or a metal case having a wall thickness of 1 mm or less may be used as the container member.
  • the thickness of the laminate film is more preferably 0.2 mm or less.
  • the wall thickness of the metal case is more preferably 0.5 mm or less, and still more preferably 0.2 mm or less.
  • the shape of the container member may be flat (thin), square, cylinder, coin, or button-shaped.
  • the container member depends on the size of the battery, and may be that for a compact battery mounted on mobile electronic devices, or a large battery mounted on two- to four-wheel automobiles.
  • the laminate film used is a multilayer film where a metal layer is sandwiched between resin layers.
  • the metal layer is preferably an aluminum foil or an aluminum alloy foil, so as to reduce weight.
  • the resin layer may be, for example, a polymeric material such as polypropylene (PP), polyethylene (PE), nylon, or polyethylene terephthalate (PET).
  • PP polypropylene
  • PE polyethylene
  • PET polyethylene terephthalate
  • the laminate film may be heat-sealed to be formed into the shape of a container member.
  • the metal case is made of aluminum or an aluminum alloy.
  • the aluminum alloy an alloy including an element such as magnesium, zinc, or silicon is preferable. If a transition metal such as iron, copper, nickel, or chromium is included in the alloy, the included amount thereof is preferably set to 100 ppm or less.
  • FIG. 3 is a cross-sectional view of a flat-form nonaqueous electrolyte secondary battery.
  • FIG. 4 is an enlarged cross-sectional view showing a portion A in FIG. 3 .
  • Each drawing is a typical view for explaining the embodiments and for promoting an understanding of the embodiments. Though there are parts different from an actual device in shape, dimension and ratio, these structural designs may be properly changed taking the following explanations and known technologies into consideration.
  • a flat-form wound electrode group 1 in flat form is housed in a bag-shaped container member 2.
  • the bag shaped container member 2 is made of a laminate film where a metal layer is sandwiched between two resin layers.
  • the flat-form wound electrode group 1 is formed by, spirally winding a stack where stacked, in order from the outside, are a negative electrode 3, a separator 4, a positive electrode 5, and a separator 4, as shown in FIG. 4 , and then press-forming the wound laminate.
  • the negative electrode 3 includes a negative electrode current collector 3a and a negative electrode layer 3b.
  • the above describe negative electrode active material is included in the negative electrode layer 3b.
  • the negative electrode 3 on the outermost side has a configuration in which a negative electrode layer 3b is formed only on one surface, which is the internal surface of a negative electrode current collector 3a, as shown in FIG. 4 .
  • the negative electrode layers 3b are formed on both of reverse surfaces of the negative electrode current collector 3a.
  • positive electrode layers 5b are formed on both of reverse surfaces of the positive electrode current collector 5a.
  • a negative electrode terminal 6 is connected to the negative electrode current collector 3a in the outermost negative electrode 3, and a positive electrode terminal 7 is connected to the positive electrode current collector 5a in the positive electrode 5 on the inner side.
  • the negative electrode terminal 6 and the positive electrode terminal 7 are extended out from the opening of the bag shaped container member 2.
  • the liquid like nonaqueous electrolyte is, for example, inserted from an opening in the bag-shaped container member 2. By heat-sealing the opening in the bag-shaped container member2, sandwiching the negative electrode terminal 6 and positive electrode terminal 7 therebetween, the wound electrode group 1 and liquid-form nonaqueous electrolyte are completely sealed in.
  • the negative electrode terminal 6 may be made of a material which is electrochemically stable at the Li insertion and extraction potential, and having electrical conductivity. Specific examples include copper, nickel, stainless steel, or aluminum.
  • the negative electrode terminal 6 is preferably made of the same material as the negative electrode current collector 3a in order to reduce the contact resistance with the negative electrode current collector 3a.
  • the positive electrode terminal 7 may be formed of, for example, a material which has electrical stability in the potential range of 3 V to 5 V (vs. Li/Li + ) relative to an oxidation-and-reduction potential of lithium, and electrical conductivity.
  • the positive electrode terminal is formed of aluminum or an aluminum alloy including Mg, Ti, Zn, Mn, Fe, Cu, Si or the like.
  • the positive electrode terminal 7 is preferably formed of the same material as the positive electrode current collector 5a in order to reduce contact resistance with the positive electrode current collector 5a.
  • the nonaqueous electrolyte battery according to the second embodiment is not limited to the configuration shown in FIGS. 2 and 3 described above.
  • the battery may be configured as shown in FIGS. 5 and 6.
  • FIG. 5 is a partially cut-out perspective view schematically showing another flat-form nonaqueous electrolyte secondary battery according to the second embodiment.
  • FIG. 6 is an enlarged cross-sectional view showing a portion B in FIG. 5 .
  • a stacked electrode group 11 is housed in the container member 12.
  • the container member 12 is made of a laminate film where a metal layer is sandwiched between two resin films.
  • the stacked electrode group 11 has a structure in which positive electrodes 13 and negative electrodes 14 are alternately stacked with a separator 15 sandwiched therebetween.
  • the electrode group 11 includes plural positive electrodes 13.
  • Each of the plural positive electrodes 13 includes a positive electrode current collector 13a, and a positive electrode layer 13b supported on both of reverse surfaces of the positive electrode current collector 13a.
  • the electrode group 11 includes plural negative electrodes 14.
  • Each of the plural negative electrodes 14 includes a negative electrode current collector 14a, and a negative electrode layer 14b supported on both of reverse surfaces of the negative electrode current collector 14a.
  • An end of the negative electrode current collector 14a of each of the negative electrodes 14 protrudes out from the negative electrode 14.
  • the protruded negative electrode current collector 14a is electrically connected to a strip-shaped negative electrode terminal 16.
  • the tip of the strip-shaped negative electrode terminal 16 is extended out from the container member 12.
  • an end of the positive electrode current collector 13a of the positive electrode 13 protrudes from the positive electrode 13 at the side opposed to the protruded end of the negative electrode current collector 14a.
  • the positive electrode current collector 13a protruding from the positive electrode 13 is electrically connected to a strip-shaped positive electrode terminal 17.
  • the tip of the strip-shaped positive electrode terminal 17 is positioned on the opposite side from the negative electrode terminal 16, and extended out from a side of the container member 12.
  • a nonaqueous electrolyte battery exhibiting having high energy density and high rapid charge-and-discharge performance, and excellent in life performance.
  • the battery pack includes one or plural of the nonaqueous electrolyte battery (unit cell) according to the second embodiment described above.
  • each of the unit cells are arranged so as to be electrically connected in series or in parallel.
  • the plural unit cells may also be connected in a combination of in a series and in parallel.
  • the plural nonaqueous electrolyte batteries can be electrically connected to structure a battery module.
  • the battery pack according to the third embodiment may include plural battery modules.
  • the battery pack according to the third embodiment may further include a protective circuit.
  • the protective circuit has a function to control charging and discharging of the nonaqueous electrolyte battery.
  • a circuit included in an equipment where the battery pack serves as a power source for example, electronic devices, vehicles, and the like may be used as the protective circuit for the battery pack.
  • the battery pack according to the third embodiment may further comprise an external power distribution terminal.
  • the external power distribution terminal is configured to externally output current from the nonaqueous electrolyte battery, and to input current to the nonaqueous electrolyte battery.
  • the current is externally provided via the external power distribution terminal.
  • the charging current including regenerative energy caused by power of vehicles such as automobiles
  • the external power distribution terminal is provided to the battery pack via the external power distribution terminal.
  • FIGS 7 and 8 One example of a battery pack 20 is shown in FIGS 7 and 8 .
  • This battery pack 20 includes plural flat-form batteries 21 having the configuration shown in FIG. 3 .
  • FIG. 7 is an exploded perspective view of an example of the battery pack 20.
  • FIG. 8 is a block diagram showing an electric circuit of the battery pack 20 of FIG. 7 .
  • Plural unit cells 21 are stacked so that the negative electrode terminals 6 and the positive electrode terminals 7 extended outside are arranged in the same direction, and fastened with an adhesive tape 22 to configure a battery module 23.
  • the unit cells 21 are electrically connected in series as shown in FIG. 8 .
  • a printed wiring board 24 is arranged to face opposite to the side plane where the negative electrode terminal 6 and the positive electrode terminal 7 of the unit cell 21 extend out from.
  • An electric insulating plate (not shown) is attached to the surface of the printed wiring board 24 facing the battery module 23 to avoid unnecessary connection of the wires of the battery module 23.
  • a positive electrode-side lead 28 is connected to the positive electrode terminal 7 located at the bottom layer of the battery module 23 and the distal end of the lead 28 is inserted into a positive electrode-side connector 29 of the printed wiring board 24 so as to be electrically connected.
  • a negative electrode-side lead 30 is connected to the negative electrode terminal 6 located at the top layer of the battery module 23 and the distal end of the lead 30 is inserted into an negative electrode-side connector 31 of the printed wiring board 24 so as to be electrically connected.
  • the connectors 29 and 31 are connected to the protective circuit 26 through wires 32 and 33 formed on the printed wiring board 24.
  • the thermistor 25 detects the temperature of the unit cells 21, and the detection signal is sent to the protective circuit 26.
  • the protective circuit 26 can shut down a plus-side wire 34a and a minus-side wire 34b between the protective circuit 26 and the energizing terminal 27 to an external device, serving as an external power distribution terminal, under a predetermined condition.
  • the predetermined condition indicates, for example, the case where the temperature detected by the thermistor 25 becomes a predetermined temperature or more.
  • Another example of the predetermined condition is when the over-charge, over-discharge, or over-current of the unit cells 21 is detected. The detection of the over-charge and the like is performed on each of the unit cells 21 or the whole of the unit cells 21.
  • the cell voltage may be detected, or positive electrode or negative electrode potential may be detected.
  • a lithium electrode to be used as a reference electrode is inserted into each of the unit cells 21.
  • wires 35 for voltage detection are connected to each of the unit cells 21. Detection signals are sent to the protective circuit 26 through the wires 35.
  • Protective sheets 36 made of rubber or resin are arranged on three side planes of the battery module 23 except the side plane from which the positive electrode terminal 7 and the negative electrode terminal 6 protrude out from.
  • the battery module 23 is housed in a housing container 37 together with each of the protective sheets 36 and the printed wiring board 24. That is, the protective sheets 36 are arranged on both internal surfaces in a long side direction and on one internal surface in a short side direction of the housing container 37.
  • the printed wiring board 24 is arranged on the internal surface on the opposite side in a short side direction.
  • the battery module 23 is located in a space surrounded by the protective sheets 36 and the printed wiring board 24.
  • a lid 38 is attached to the upper surface of the housing container 37.
  • a heat-shrinkable tape may be used in place of the adhesive tape 22.
  • the battery module is bound by placing the protective sheets on the both sides of the battery module, revolving the heat-shrinkable tape, and thermally shrinking the heat-shrinkable tape.
  • connection in series may be combined with connection in parallel.
  • Assembled battery packs may be connected further in series or in parallel.
  • the battery pack shown in FIGS. 7 and 8 include plural unit cells 21, the battery pack according to the third embodiment may include only one unit cell 21.
  • the aspect of the battery pack may be appropriately changed depending on its application.
  • the battery pack according to the embodiment can be suitably used in applications in which cycle performance is demanded to be excellent when large current is taken out.
  • the battery pack is used as a power source of a digital camera, or for example, a battery for mounting on a vehicle such as a two- to four-wheeled hybrid electric automobiles, a two-to four-wheeled electric automobiles or a power-assisted bicycle.
  • the battery pack is suitably used for a battery mounted on a vehicle.
  • the battery pack is configured, for example, to recover regenerative energy caused by power of the vehicle.
  • the vehicle include two to four-wheeled hybrid electric automobiles, two to four-wheeled electric automobiles, electric assist bicycles, and electric trains.
  • FIG. 9 shows an example of an automobile that includes a battery pack according to the third embodiment.
  • the automobile 41 shown in FIG. 9 includes a battery pack 42, which is an example of the battery pack according to the third embodiment, mounted in its engine room.
  • the mounting position is not limited to engine rooms.
  • the battery pack may also be mounted in rear parts of automobiles or under seats.
  • a battery pack having high energy density and high rapid charge-and-discharge performance, and excellent in life performance.
  • Example 1 powders of commercially available oxide and carbonate reagents shown in Table 1 were weighed at the indicated raw material mixing ratio and put in a mortar.
  • TiO 2 as a Ti source, Nb 2 O 5 as an Nb source, and Na 2 CO 3 as an M(I) source were put in a mortar such that the mixing ratio was 1.0 : 1.153 : 0.0139.
  • Nb 2 O 5 is the Nb source in a finally obtained product and at the same time an M(V) source.
  • ethanol was added to the mortar into which the raw material powders were put, and then wet mixing was performed.
  • the thus obtained mixture was set in an electric furnace (box-type muffle furnace) and subjected to heating treatment, as described in Table 2. Specifically, preliminary calcining was first performed at a temperature of 850°C for 6 hours. Subsequently, a preliminarily calcined powder was taken out from the furnace, pulverized again, and then, mixed further.
  • an electric furnace box-type muffle furnace
  • the calcined powder which had been mixed again, was placed into the furnace and subjected to second calcining at a temperature of 1100°C for 6 hours. After calcining, the calcined powder was taken out from the furnace and then mixed again.
  • the calcined powder which had been mixed again, was placed into the furnace and subjected to third calcining at a temperature of 1100°C for 12 hours. At this time, the powder, for which calcining at a temperature of 1100°C had finished, was immediately taken out from the electric furnace and allowed to cool at room temperature in the air.
  • Example 21 To the thus obtained mixture, first calcining was successively performed at a temperature of 1100°C for 12 hours. After calcining, the calcined powder was taken out from the furnace and then mixed again.
  • the calcined powder which had been mixed again, was placed into the furnace and subjected to second firing at a temperature of 1100°C for 6 hours. After calcining, the calcined powder was taken out from the furnace and then mixed again.
  • the calcined powder which had been mixed again, was placed into the furnace and subjected to third calcining at a temperature of 1100°C for 6 hours. At this time, the powder, to which calcining at a temperature of 1100°C had finished, was immediately taken out from the electric furnace, and then allowed to cool at room temperature in the air, thereby obtaining an active material of Example 21.
  • Example 22 to a mixture obtained by re-pulverization and mixing after preliminary calcining, first calcining was similarly performed at a temperature of 1200°C for 6 hours. After calcining, the calcined powder was taken out from the furnace and then mixed again.
  • the calcined powder which had been mixed again, was placed into the furnace and subjected to second calcining at a temperature of 1200°C for 12 hours.
  • the powder to which calcining at a temperature of 1200°C had finished was immediately taken out from the electric furnace and allowed to cool at room temperature in the air, thereby obtaining an active material of Example 22.
  • Comparative Example 1 a monoclinic composite oxide TiNb 2 O 7 was synthesized using a method similar to the method described in Jpn. Pat. Appln. KOKAI Publication No. 2012-99287 .
  • the synthesis was performed as follows. First, a titanium oxide powder and a niobium pentoxide powder were weighed at a molar ratio of 1 : 1. The weighed raw material powders were put into a mortar. Ethanol was added to the mortar, and then wet mixing was performed. The mixture thus obtained was put into a platinum crucible, calcined at a temperature of 1100°C continuously for 20 hours, and after that, the calcined mixture was cooled slowly in the furnace, whereby an active material in Comparative Example 1 was obtained. At this time, about three hours was spent to reduce the in-furnace temperature of the box-type muffle furnace from 1100°C to 100°C.
  • Comparative Example 2 raw material powders were mixed at a mixing ratio similar to that in the method described in Example 1. After the thus obtained mixture was calcined at a temperature of 1100°C continuously for 20 hours as in Comparative Example 1, the calcined mixture was cooled slowly in the furnace, whereby an active material in Comparative Example 2 was obtained.
  • Comparative Example 3 a raw material powders were mixed at a mixing ratio similar to that in the method described in Example 1. The mixture was preliminarily calcined at a temperature of 850°C for 6 hours. Subsequently, a preliminarily calcined powder was taken out from the furnace, pulverized again, and then, further mixed.
  • the calcined powder which had been mixed again, was placed into the furnace and subjected to second calcining at a temperature of 1100°C for 6 hours. After calcining, the calcined powder was taken out from the furnace and then mixed again.
  • the calcined powder which had been mixed again, was placed into the furnace and subjected to third calcining at a temperature of 1100°C for 12 hours. After that, the calcined powder was cooled slowly in the furnace without being immediately taken out from the electric furnace, whereby an active material in Comparative Example 3 was obtained.
  • Comparative Example 4 raw material powders were mixed at a mixing ratio similar to that in the method described in Example 1. First, the mixture was preliminarily calcined at a temperature of 850°C for 6 hours. Subsequently, the preliminarily calcined powder was taken out from the furnace, pulverized again, and then, further mixed.
  • the calcined powder which had been mixed again, was placed into the furnace and subjected to second calcining at a temperature of 1100°C for 6 hours. After calcining, the calcined powder was taken out from the furnace and then mixed again.
  • the calcined powder which had been mixed again, was placed into the furnace and subjected to third calcining at a temperature of 1100°C for 12 hours. After that, the calcined powder was cooled slowly in the furnace, and then again at 600°C for 6 hours, an annealing treatment was performed, whereby an active material in Comparative Example 4 was obtained.
  • compositions of the active materials obtained in Examples 1 to 22 and Comparative Examples 1 to 4 were analyzed by ICP. As a result, it was confirmed that the element ratios were the same as the intended element ratios described in Tables 1, 3, and 5.
  • the active materials obtained in Examples 1 to 22 and Comparative Examples 1 to 4 were measured by a powder X-ray diffraction method using Cu-K ⁇ rays, as described above. Thus, an X-ray diffraction pattern of each of the active materials obtained in Examples 1 to 22 and Comparative Examples 1 to 4 was obtained. For the measurement, each active material was pulverized until the average particle diameter of a sample of the active material was reduced to approximately 10 um.
  • Example 2 10 parts by mass of acetylene black as a conductive agent was mixed with 100 parts by mass of the active material obtained in Example 1 to obtain a mixture. Then, the mixture was dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a dispersion liquid. 10 parts by mass of polyvinylidene-fluoride (PVdF) as a binder was mixed with this dispersion liquid based on 100 parts by mass of the active material to produce an electrode slurry. The slurry was applied onto a current collector formed of aluminum foil using a blade. The slurry on the current collector was dried at 130°C for 12 hours under vacuum to obtain an electrode.
  • NMP N-methyl-2-pyrrolidone
  • PVdF polyvinylidene-fluoride
  • the electrochemical measurement cell of Example 1 was manufactured using the above electrode, metal lithium foil as a counter electrode, and nonaqueous electrolyte.
  • a nonaqueous electrolyte a nonaqueous electrolyte in which lithium hexafluorophosphate (LiPF 6 ) was dissolved at a concentration of 1 M in a mixed solvent (volume ratio 1 : 1) of ethylene carbonate and diethyl carbonate was used.
  • Example 1 The electrochemical measurement cell of Example 1 was subjected to charge and discharge test at room temperature. The charge and discharge test was conducted at a charge-and-discharge current value of 0.2 C (discharge rate) within a potential range of 1.0 V to 3.0 V relative to the metallic lithium electrode. At this time, an initial discharge capacity was measured. The initial discharge capacity in Example 1 was 278 mAh/g.
  • Example 1 For the electrochemical measurement cell of Example 1, the discharge capacity (0.2 C discharge capacity) at a discharge current of 0.2 C and the discharge capacity (5.0 C discharge capacity) at a discharge current of 5.0 C were measured. By dividing the 5.0 C discharge capacity, which was obtained by measurement, by the 0.2 C discharge capacity, which was similarly obtained by measurement, a 5.0 C discharge capacity/0.2 C discharge capacity ratio was calculated. A 5 C discharge capacity retention ratio (vs. 0.2 C capacity) thus obtained is indicative of rate performance.
  • Example 1 In order to examine whether the active material obtained in Example 1 can be charged and discharged stably, for the electrochemical measurement cell of Example 1, charging and discharging were repeated for 100 cycles. One cycle was set to be charging once and discharging once. Charging and discharging were performed at room temperature at a current value of 1 C (discharge rate) within a potential range of 1.0 V to 3.0 V relative to the metallic lithium electrode.
  • the discharge capacity retention ratio after 100 cycles was examined as follows. For the electrochemical measurement cell of Example 1, after charging and discharging were repeated for 100 cycles, charging and discharging were performed again at 0.2 C (time discharge rate), and thus the discharge capacity after 100 cycles was obtained.
  • the discharge capacity retention ratio was calculated, setting the initial discharge capacity as 100%. That is, by dividing a value of the discharge capacity after 100 cycles by a value of the initial discharge capacity, the discharge capacity retention ratio after 100 cycles was calculated.
  • the discharge capacity retention ratio thus obtained is indicative of cycle performance of the active material, that is, life performance.
  • electrochemical measurement cells of Examples 2 to 22 and Comparative Examples 1 to 4 were manufactured using the active materials obtained in Examples 2 to 22 and the active materials obtained in Comparative Examples 1 to 4.
  • measurement was performed in the same manner as in the electrochemical measurement for the electrochemical measurement cell of Example 1. The results are shown below in Table 7.
  • an active material including a monoclinic niobium-titanium composite oxide is provided.
  • the active material a portion of or all of niobium or titanium as a constituent element of Nb 2 TiO 7 is substituted by an element such that any one of the following formulas (1) to (3) is satisfied: Ti(IV) ⁇ 0.75M(V) + 0.25M(I) (1) Ti(IV) ⁇ 0.6M(VI) + 0.4M(I) (2) Nb(V) ⁇ 0.8M(VI) + 0.2M(I) (3), where M(VI) is at least one of Mo and W, M(V) is at least one of Nb, Ta, and V, and M(I) is at least one of Na, K, Rb, and Cs.
  • M(VI) may be either one of Mo and W, or a combination of both Mo and W.
  • M(V) may be one of Nb, Ta, and V, or a combination of two or more of Nb, Ta, and V.
  • M(I) may be one of Na, K, Rb, and Cs, or a combination of two or more of Na, K, Rb, and Cs.
  • this active material can realize a nonaqueous electrolyte battery which can exhibit both excellent rapid charge-and-discharge performances and excellent repetitive charge-and-discharge performances.

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Claims (17)

  1. Matériau actif comprenant un oxyde composite monoclinique de niobium-titane dans lequel une partie ou la totalité du niobium (Nb) ou du titane (Ti) en tant qu'élément constitutif de Nb2TiO7 est remplacée par un élément de telle sorte que l'une quelconque des formules (1) à (3) suivantes est satisfaite :

            Ti (IV) → 0,75 M (V) + 0,25 M (I)     (1)

            Ti (IV) →0,6 M (VI) + 0,4 M (I)     (2)

            Nb (V) →0,8 M (VI) + 0,2 M (I)     (3),

    dans lequel M(VI) est au moins l'un de Mo et W, M(V) est au moins l'un de Nb, Ta et V, et M(I) est au moins l'un de Na, K, Rb et Cs.
  2. Matériau actif selon la revendication 1, dans lequel l'oxyde composite monoclinique de niobium-titane est représenté par l'une quelconque des formules générales (A) à (E) suivantes :

            Nb2Ti1-y(M(V)0,75M(I)0,25)yO7     (A)

            Nb2Ti1-y(M(VI)0,6M(I)0,4)yO7     (B)

            Nb2-x(M(VI)0,8M(I)0,2)xTiO7     (C)

            Nb2-x(M(VI)0,8M(I)0,2)xTi1-y(M(V)0,75M(I)0,25)yO7     (D)

            Nb2-X(M(VI)0,8M(I)0,2)xTi1-y(M(VI)0,6M(I)0,4)yO7     (E)

    dans lequel M(VI) est au moins l'un de Mo et W, M(V) est au moins l'un de Nb, Ta et V, M(I) est au moins l'un de Na, K, Rb, et Cs, 0 <x ≤ 1, et 0 <y ≤ 1.
  3. Matériau actif selon la revendication 2, dans lequel 0 < y < 1 dans les formules générales (A), (B), (D) et (E).
  4. Matériau actif selon la revendication 2, dans lequel 0,1 ≤ y ≤ 0,9 dans les formules générales (A), (B), (D) et (E).
  5. Matériau actif selon la revendication 2, dans lequel 0,1 ≤ x ≤ 1,0 dans les formules générales (C), (D) et (E).
  6. Matériau actif selon la revendication 1, caractérisé en ce que l'oxyde composite monoclinique de niobium-titane est représenté par l'une quelconque des formules générales suivantes (A') à (E') :

            LiaNb2T1-y(M(V)0,75M(I)0,25)yO7     (A')

            LiaNb2Ti1-y(M(VI)0,6M(I)0,4)yO7     (B')

            LiaNb2-x(M(VI)0,8M(I)0,2)xTiO7     (C')

            LiaNb2-x(M(VI)0,8M(I)0,2)xTi1-y(M(V)0,75M(I)0,25)yO7     (D')

            LiaNb2-x(M(VI)0,8M(I)0,2)xTil-y(M(VI)0,6M(I)0,4)yO7     (E'),

    dans lequel M(VI) est au moins l'un de Mo et W, M(V) est au moins l'un de Nb, Ta et V, M(I) est au moins l'un de Na, K, Rb, et Cs, 0 <x ≤ 1, 0 <y ≤ 1 et 0 ≤ a ≤ 5.
  7. Matériau actif selon la revendication 6, dans lequel 0 < y < 1 dans les formules générales (A'), (B'), (D') et (E').
  8. Matériau actif selon la revendication 6, dans lequel 0,1 ≤ y ≤ 0,9 dans les formules générales (A'), (B'), (D') et (E').
  9. Matériau actif selon la revendication 6, dans lequel 0,1 ≤ x ≤ 1,0 dans les formules générales (C), (D) et (E).
  10. Matériau actif selon la revendication 1, dans lequel dans l'oxyde composite monoclinique de niobium-titane, une partie du titane est substituée par au moins l'un de Zr, Hf, Ge et Sn.
  11. Matériau actif selon la revendication 1, dans lequel dans l'oxyde composite monoclinique de niobium-titane, une partie du titane est substituée par au moins l'un de Zr, Hf et Ge, de telle sorte qu'une quantité de substitution par rapport aux sites de Ti d'une structure cristalline de l'oxyde composite monoclinique de niobium-titane est une moitié ou moins.
  12. Batterie à électrolyte non aqueux comprenant :
    une électrode négative (3) comprenant le matériau actif selon l'une quelconque des revendications 1 à 11 ;
    une électrode positive (5) ; et
    un électrolyte non aqueux.
  13. Bloc-batterie (20) comprenant la batterie à électrolyte non aqueux selon la revendication 12.
  14. Bloc-batterie (20) selon la revendication 13, dans lequel le bloc-batterie comprend en outre un circuit de protection (26) et une borne de distribution de courant externe.
  15. Bloc-batterie selon la revendication 13 ou 14, dans lequel le bloc-batterie (20) comprend plusieurs batteries à électrolyte non aqueux (21), chacune selon la revendication 12, dans lequel les plusieurs batteries à électrolyte non aqueux (21) sont connectées électriquement en série, en parallèle, ou dans une combinaison en série et en parallèle.
  16. Véhicule (41) sur lequel est monté le bloc-batterie (42) selon l'une quelconque des revendications 13 à 15.
  17. Véhicule (41) selon la revendication 16, dans lequel le bloc-batterie (42) est configuré pour récupérer une énergie régénératrice d'un courant du véhicule.
EP16187789.9A 2015-09-14 2016-09-08 Matériau actif, batterie électrolytique non aqueuse, module de batterie, bloc-batterie et véhicule Active EP3141527B1 (fr)

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JP6980587B2 (ja) 2018-03-23 2021-12-15 株式会社東芝 電極、二次電池、電池パック、及び車両
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TWI705952B (zh) * 2018-11-06 2020-10-01 財團法人工業技術研究院 摻雜鈮酸鈦與電池
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EP4059892B1 (fr) * 2021-03-17 2023-12-13 Kabushiki Kaisha Toshiba Matériau actif, électrode, batterie secondaire, bloc-batterie et véhicule
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